Note: Descriptions are shown in the official language in which they were submitted.
This invention relates to a method of separation
of a gas from a gas mixture as applicable in particular to
the purification of uranium hexafluoride derived from an
isotopic enrichment plant.
It is known that, in the petrochemical industry,
problems often have to be solved in regard to the separa-
tion of gas mixtures. For example at the outlet of a
gas-phase synthesis reactor, it may be required to collect
the synthesis gas and to recover the reaction gases which
have not reacted in order to recycle these latter in
another reactor together with a make-up or supplement gas.
It may also be necessary to carry out purification or
concentration of a gas in a synthetic or natural mixture.
In order to separate gas mixtures of this type, known
separation processes include the following :
- condensation : the gas mixture is cooled in heat
exchangers and in atmospheric coolants, then in partial
condensers,
- absorption : the mixture is cooled and selectively
absorbed on molecular sieves,
- dissolution : the mixture is cooled and selectively
dissolved in suitable solvents.
These processes are subject to disadvantages from
an economic standpoint since they are costly and presuppose
considerable capital investments ; moreover, from a thermo-
dynamic point of view, they call for the use of a large
amount of mechanical or heating energy.
In regard to the purification of uranium hexa-
--2--
fluoride delivered by an isotopic enrichment plant, it is-
known that uranium hexafluoride contains a certain number
of impurities such as F2, ClF3, HF, ClF, N2, etc...
The separation of UF6 from these light gases is
usually performed by methods such as :
- crystallization : the gas mixture is cooled in heat
exchangers or crystallizers, thus resulting in crystal-
lization of the UF6. It is necessary to have banks of
these crystallizers in series in order to prevent
trapping o~ the light gases at the time of excessively
rapid formation of UF6 crystals and at the same time in
order to permit of continuous purification. The
different steps of cooling, reheating and vaporization
which are necessary consume energy and leave the gases
and vapors in contact with each other over long periods
of time ;
- distillation : this process is continuous but is fairly
dlfficult to control and problems arise from the need to
handle the overheated corrosive liquids which are present
in this case ;
- the use of cascade-connected gaseous diffusion barriers :
this process makes it possible to obtain fairly high
separation factors but entails considerable power
consumption without thereby permitting complete
separation.
In order to separate a binary gas mixture,
especially a mixture of hydrogen and sulphur dioxide, it
has also been endeavored to utilize the phenomenon of
1`-
capillary condensation in the vicinity of a porous mass
of graphite powder by modifying the conditions of tempera-
ture and pressure. This method didnot prove satisfactory,
however, since the graphite powder employed did not really
make it possible to obtain an appreciable continuous flow
of the sulphur dioxide through its mass and did not really
constitute a physical barrier for the hydrogen of the
mixture.
The precise object of the present invention is
to provide a method of separation of a gas fro~ a gas
mixture which overcomes the disadvantages of all the
methods recalled in the foregoing and makes it possible
to obtain a continuous and efficient separation of the
gases which are present.
The method according to the invention for the
separation of a gas from a gas mixture in which said gas
is the most readily condensable of the gases of the
mixture essentially consists in passing said gas mixture
in contact with at least one microporous barrier having
a permeability between lO0 x 10 7 and 1000 x 10 7 moles
of air/cm2/min./cmHg, a thickness between a few microns
and a few tens of microns and pore radii between lO and
lO0 A; the partial pressure of said most readily
condensable gas and/or the temperature of said gas
mixture is adjusted as a function of the mean pore
radius of said barrier in order to ensure capillary
condensation of said most readily condensable gas at
the pore inlets of said barrier and a flow of said
condensed gas along the pores and across said barrier and
~,~
, i .
said gas which has thus condensed is then collected.
In accordance with the invention, the micro-
porous barriers are of metal, of ceramic material or of
fluorinated polymer. The unit of permeability of these
microporous elements as expressed in moles of air/cm2/min/
cmHg means that x moles of air pass at a temperature of
20C per cm2 of microporous element surface area per minu~e
and in respect of a pressure diference of 1 cmHg between
the exterior and the interior of the microporous element.
The phenomenon of capillary condensation employed
in the method according to the invention is carried into
effect in accordance with Kelvin's law :
Pv ~ M
g P pL.R~T.m
wherein :
Pv = saturated vapor pressure at the temperature T,
P = partial vapor pxessure in the mixture,
a = surface tension of the condensate,
M = molar mass of the condensate,
PL = specific volume of the condensate
R = ideal gas constant,
m = radius of curvature of the meniscus.
It is recalled that the radius of curvature m
of the meniscus of the condensate as given by the Kelvin
relation and the corresponding pore radius yp assumed to
be cylindrical are related by the following relation :
YP
--5--
where ~ corresponds to the angle of contact of the
condensate with the wall of the pore. This relation
clearly points to the importance of wettability of the
condensate with respect to the material which constitutes
the barriers.
The nature of the microporous barriers employed
in accordance with the method of the invention as well as
their characteristics (permeability, thickness, pore
radius) make it possible to obtain a continuous and
selective flow of the most readily condensable gas and
-- - therefore eficient separation; -In fa~t, the pores of the
microporous layer are completely obstructed by the con-
densate and thus constitute a barrier for the other gases
which are noncondensable or less readily condensable than
the first gas.
The application of the method in àccordance with
the invention to the purification of uranium hexafluoride
obtained from an isotopic separation plant is particularly
advantageous. In fact, uranium hexafluoride is far more
~0 readily condensable than the other gases constituting
impurities which accompany UF6 at the outlet of an isotopic
enrichment plant. Thus, in accordance with the method o~
the invention, the pores of the microporous layer are
rapidly clogged by the condensed uranium hexafluoride and
form a barrier for the other gases which constitute the
impurities. Moreover, by virtue of the method according
to the invention, the contacting time between the condensed
llquid and the mixture to be separated is reduced to a very
considerable extent: the possibilities of dissolution of
the other gases in liquid UF6 are in that case very
limited. The rates of permeation in accordance with the
method of the invention are considerably higher than those
obtained when UF6 is purified by gaseous diffusion. Thus
the ratio is between 5 and 10 according to the microporous
element employed.
In order to ensure efficacious purification of
UF6 in accordance with the method of the invention, steps
are taken to ensure that the mixture is entirely and con-
tinuously homogeneous and that the conditions of partial
pressure of UF6 are uniform throughout the length of the
microporous element employed.
By way of example and without any limitation
! being implied, the description given below relates to the
practical application of the method in accordance with the
invèntion to the purification of uranium hexafluoride
derived from an isotopic enrichment plant.
The accompan~ing figure is a diagrammatic
illustration of the device for carrying out the method
contemplated in the present Application.
A mixture of UF6 and ClF3 is ~ithdrawn through
the duct 1 at a rate of 2500 g/.5 at the level of the stage
n of an isotopic enrichment plant at the point correspond-
ing to the highest pressure. The proportions of the
mixture are 7.1 moles of UF6 for 0.11 mole of ClF3. The
pressure is 1500 millibars and the temperature is higher
than 100C.
1~ ~5~
This mixture is passed into a heat exchanger 2 and
cooled therein to a temperature of 90C, then passed
through the duct 3 into the diffuser 4 which comprises
540 microporous barriers.
At the outlet of said diffuser 4, practically pure
UF6 is delivered through the pipe 5 at a flow rate of
2400 g/s, namely 6.95 moles/second of UF6; the temperature
is 90C and the pressure is 275 millibars. This uranium
hexafluoride is sufficiently free of impurities to permit
10 withdrawal at 6 of the quantity desired for pxoduction and
to reintroduce the remainder at 7 for feeding back to the
stage n of the enrichment plant at a point corresponding
to the lowest pressure.
At the outlet of the diffuser 4, a mixture of UF6 and
r ClF3 is obtained through the duct ~ in proportions of
0.13 mole of UF6 in respect of 0.11 mole of ClF3 ; the
temperature is 90C and the pressure is 1450 millibars.
This mixture is cooled to a temperature of 75C by
passing through the heat exchanger 9, then introduced
20 through the duct 10 into the diffuser 11 which is constit-
uted by 50 microporous barriers.
At the outlet of said diffuser 11, practically pure
~F6 is obtained through the duct 12 at a flow rate of
35 g/s, namely 0.10 mole/s of UF6 ; the temperature is 75C,
the pressure is 275 millibars. It is possible either to
effect a further withdrawal of said uranium hexafluoride
for production or to reintroduce this latter into the stage
n of the enrichment plant at a point corresponding to low
1~.15~
pressure.
At the outlet of the diffuser 11, a mixture of ClF2
and uranium hexafluoride is obtained through the duct 13 in
proportions of o.ll mole of ClF3 in respect of 0.03 mole of
UF6; the temperature is 75C, the pressure is 1400 milli-
bars. This final mixture which therefore contains approx-
imately 20 % UF6 and 80 % ClF3 can either be discharged or
undergo further separation by means of conventional methods
such as condensation or undergo further separation by means
of the method in accordance with the invention.
The barriers of the diffuser 4 and of the difuser 11
are tubular barriers of ceramic material and have a dia-
meter of 1~5 cm, a pore radius of 25 A and a sweep length
of 1 m. The barriers are placed in parallel in each
diffuser. Barriers having the same dimensions and either
metallic or of fluorinated polymer have also been employed
with comparable results.
By way of comparison, it can be noted that separation
of the same mixture by means of the conventional method of
gaseous diffusion would entail the need for approximately
twenty stages and that each stage calls for a compression
o the entire flow and approximately five times the number
of barriers per diffuser.
Compared with the conventional methods of separation
by crystallization steps, the method in accordance with the
invention offers the following advantages :
- the products are available at pressures which can be
directly utilized either for pro~uctioA or ~or recy ling
- ~
-
in thè cascade ;
the set of two diffusers replaces the first bank of
crystallizers and has the further advantage of dispensing
with the need for an evaporator ;
in the method according to the invention, approximately
35 x 103 kcal/h are required for cooling purposes
whereas 100 x 10 kcal/h are necessary for cooling in
accordance with the crystallizer process ;
the process is continuous and avoids the need for
storages of crystallized products.
.
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